Charge-Transfer Salts of Electron-Rich Diruthenium and Macrocyclic Tetraruthenium Complexes

本项目的目的是合成和详细表征双核和大环四钌配合物与扩大，π共轭连接及其电荷转移盐。构建这些络合物，使得当与适当的强有机电子受体如四卤代苯并醌X4 BQ或四氰基-对-醌二甲醚TCNQ和F4 TCNQ组合时，需要产生具有π-堆叠结构的导电电荷转移盐的结构和电子先决条件。特别是，我们将调查所得的电荷转移盐相对于其离子性（即。e.供体/受体处的正/负电荷的分数）以及它们的光学、电子和磁性。通过分析钌链烯基给体的Ru（CO）振动能和有机受体的CO和CN伸缩频率的变化，以及对它们的电子光谱和电子顺磁共振谱中的电荷转移带进行分析，我们将获得关于有机金属给体和有机受体之间电荷转移程度的详细信息。我们还将解决的重要问题，如何的电荷转移盐的离子性和结构取决于供体和受体的化学计量比和它们的内在氧化还原电位。

The aim of this project is the synthesis and detailed characterisation of dinuclear and macrocyclic tetraruthenium complexes with expanded, pi-conjugated linkers and of their charge transfer salts. These complexes are constructed such as to entail the structural and electronic prerequisites for generating electrically conductive charge transfer salts with pi-stacked structures when combinded with appropriate strong organic electron acceptors such as tetrahalogenated bezoquinones X4BQ or tetracyano-para-quinodimethanes TCNQ and F4TCNQ. In particular, we will investigate the resulting charge-transfer salts with respect to their ionicity (i. e. the fraction of positive / negative charge at the donor / acceptor) and their optical, electronic and magnetic properties. We will obtain detailed information as to the extent of charge transfer between the organometallic donor and the organic acceptor by analyzing the changes of the Ru(CO) vibrational energies of the ruthenium alkenyl donors and of the CO and CN stretching frequencies of the organic acceptor as well as by srutinizing the charge transfer bands in their electronic spectra and electronic paramagnetic resonance spectra. We will also address the important question of how the ionicities and structures of the charge transfer salts depend on the stoichiometric ratio of the donor and the acceptor and their intrinsic redox potentials.